Fuel 368 (2024) 131636

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Full Length Article

Ignition characteristics of ammonia-methanol blended fuel in a rapid

compression machine
Qihang Zhang , Ridong Zhang , Yunliang Qi , Zhi Wang *
School of Vehicle and Mobility, Tsinghua University, Beijing 100084, China

A R T I C L E I N F O A B S T R A C T

Keywords: Ammonia has attracted wide attention in recent years as a carbon-free fuel. However, the low reactivity and
Ammonia combustion inertness of ammonia pose challenges to its applications in engines. Adding highly reactive fuels,
Methanol such as renewable carbon–neutral methanol, offers a potential solution. To investigate the ignition characteristics
Ignition delay time
of ammonia-methanol blended fuel, ignition delay time measurement and fast gas sampling under stoichiometric
Sampling
conditions with four ammonia blending ratios (20 % ammonia, A20; 40 % ammonia, A40; 80 % ammonia, A80;
Intermediate species
95 % ammonia, A95) were carried out on a rapid compression machine under engine-relevant conditions. The
effective thermodynamic conditions were 15–25 bar and 810–970 K. The concentrations of fuels NH3, CH3OH,
and intermediate species N2O, CO, as well as products N2, CO2 were detected using gas chromatography.
Chemical analysis was performed based on simulations using five ammonia-methanol reaction mechanisms. The
ignition delay time results showed that the addition of methanol shortened the ignition delay time, with only a
little change in ignition delay time beyond 20 % methanol content. Methanol significantly promoted the pro­
duction of OH radical, leading to the enhancement of the overall mixture reactivity. The sampling results showed
different consumption patterns of ammonia and methanol during the ignition process at different mixing ratios.
For A80, methanol was consumed from the early stage of the ignition process, while ammonia consumption was
negligible in the early stage. Conversely, for A95, ammonia consumption began in the early stage. This suggests
that methanol and its intermediate species inhibited the consumption of ammonia, however, ammonia promoted
the consumption of methanol. Chemical analysis further revealed that the inhibitory effect of methanol on
ammonia consumption was weakened with the decrease of methanol proportion.

1. Introduction
In recent years, the intensification of global climate change has led to
the implementation of stricter international emission regulations and
the adoption of carbon reduction policies. Consequently, carbon–neutral
fuels emerged as a promising solution [1–3], with ammonia and
hydrogen gaining significant attention as carbon-free alternatives.
Compared to hydrogen, ammonia offers several advantages due to its
mature production chain, well-developed infrastructure, lower storage
and transportation costs, and most notably, its inherent safety in terms
of being less prone to explosions [4–6]. However, the low reactivity and
combustion inertness of ammonia limit its use as a single fuel in engines
[5,6]. To overcome this limitation, ammonia is commonly blended with
highly reactive fuels such as hydrogen, methane, and dimethyl ether
(DME) [7–13]. Among highly reactive fuels, methanol is uniquely ad­
vantageous for its large ammonia solubility [14]. Additionally,
methanol is a fuel that can exist in liquid form under normal atmo­
spheric conditions, which makes it easier to store and transport
compared to methane and hydrogen [1,15]. These features facilitate the
easy blending of ammonia and methanol in liquid form for convenient
filling and use. Moreover, methanol can be produced through carbon
capture technology or biomass technology [15,16], thereby achieving
carbon neutrality.
The combustion of blended fuels is complicated. The investigation
conducted by Dai et al. [9] indicated that hydrogen strongly enhanced
the ignition process of ammonia, particularly in the formation and
decomposition of hydrogen peroxide, but hydrogen did not affect the
oxidation path of ammonia. Another study of Dai et al. [8] reported a
similar ignition-enhancing effect of methane on ammonia. They found
that ammonia was involved in methane consumption process through
the reaction CH4 + NH2 = CH3 + NH3. Meng et al. [13] investigated the
combustion and emission of ammonia/DME dual-fuel, finding that DME

* Corresponding author.
E-mail address: wangzhi@tsinghua.edu.cn (Z. Wang).

https://doi.org/10.1016/j.fuel.2024.131636
Received 7 January 2024; Received in revised form 26 March 2024; Accepted 1 April 2024
Available online 6 April 2024
0016-2361/© 2024 Elsevier Ltd. All rights reserved.
Q. Zhang et al.
improved the combustion progress of ammonia. The addition of DME
increased the production of NO by yielding CH3 radicals, which also
influenced the oxidation path of ammonia. These investigations
demonstrate that although additives can improve the ignition perfor­
mance of ammonia, different additives can interact with ammonia in
various ways and have distinct effects on the oxidation process, leading
to complex ignition characteristics for blended fuels. Similar work can
be found in Refs. [17–19]. Although the combustion characteristics and
engine performance of methanol blended with traditional hydrocarbon
fuels have been widely studied [20–24], its blending with ammonia
remains inadequately explored.
Previous studies have shown that the addition of methanol can
promote the combustion of ammonia. Wang et al. [25] used the heat flux
method to measure the laminar burning velocity of ammonia-methanol
mixture at 298–448 K. They found that the addition of methanol to
ammonia had a similar promotion effect on the laminar burning velocity
as hydrogen and methane. Xu et al. [18] conducted a numerical inves­
tigation on the combustion characteristics of ammonia-methanol
mixture, revealing that the addition of methanol has a strong
combustion-promoting effect. Compared with pure ammonia, the peak
laminar burning velocity increased by 60 % when 20 % methanol was
added. Li et al. [26] studied the ignition delay time of ammonia-
methanol mixture using a shock tube at temperatures of 1250–2150 K
and pressures of 0.14 and 1.0 MPa, based on which they developed a
simplified mechanism for chemical kinetics analysis. They concluded
that adding 5 % methanol could shorten the ignition delay time of
ammonia-methanol mixture by more than 60 %. The ignition delay time
of ammonia-methanol mixture was mainly affected by small radicals,
such as OH, O, HO2 and H. More studies on ammonia-methanol can be
found in Refs. [27,28].
While the above studies provide valuable insights, their conditions
differ from those (medium to high temperature and high pressure)
required for ammonia use in internal combustion engines. Li et al. [29]
used a rapid compression machine to measure the ignition delay time of
ammonia-methanol mixtures at temperatures ranging from 845 K to
1100 K and pressures of 20 and 40 bar. The experimental results
demonstrated that the addition of methanol enhanced the reactivity of
the mixture. Then they developed a chemical reaction mechanism for
ammonia-methanol and conducted a kinetic analysis. The results
revealed that the addition of methanol enriched the O/H radical pool
through different reaction pathways, leading to the consumption of
ammonia and promoting auto-ignition. Nevertheless, their investigation
paid little attention to the interaction between ammonia, methanol and
their intermediate species, which plays an important role in the ignition
process of the blended fuel, as mentioned earlier. The data of species
concentration during the ignition of ammonia-methanol mixture have
not been reported in previous works, which will provide strong support
for the study of C-N interaction reaction. Therefore, the detailed ignition
characteristics of ammonia-methanol blended fuel needs to be further
studied.
Under such a background, in the current work, ignition delay time
measurement and fast gas-sampling experiments of the ammonia-
methanol blended fuel were carried out on a rapid compression ma­
chine under engine-relevant conditions. Simulations using ammonia-
methanol chemical mechanisms were also performed, based on which,
chemical analysis was conducted. After introducing the experimental
setup and model validation, the study elucidates the ignition-enhancing
effect of methanol on ammonia, the fuel consumption patterns of the
blended mixture, and the interactive reaction paths of ammonia and
methanol.
2. Experimental setup
2.1. RCM system
The experiments were conducted in a rapid compression machine at
2
Fuel 368 (2024) 131636
Tsinghua University (TU-RCM), as shown in Fig. 1. An optimized crev­
iced piston was used in the TU-RCM to eliminate temperature in­
homogeneity. The premixed mixture in the combustion chamber was
compressed within 25–30 ms. Further details on the description and
functioning of the TU-RCM can be found in Refs. [30,31].
2.2. Sampling system and gas chromatography
A fast gas-sampling system coupled with the RCM was used to take a
small portion of reacting gas and freeze the intermediate species during
the compression ignition process of ammonia-methanol mixture. The
sampling system comprised a sampling probe, a solenoid valve (Parker
Series 9), a sampling chamber equipped with a pressure sensor (Kistler
4045A), a laser trigger system (consisting of a laser sensor and a signal
generator RIGOL DG2052), a vacuum pump (Agilent DS 102), and
vacuum tubes, as depicted in Fig. 1. Positioned to protrude 2 mm from
the inner wall of the combustion chamber, the sampling probe facili­
tated sampling from the ’adiabatic core region’ of the reacting gas [32].
Before each test, the sampling system was vacuumized to less than
0.01 Torr and the solenoid valve remained closed. At predetermined
time after the EOC, the sampling solenoid valve would be opened for a
fixed duration (4 ms in this work) under the control of the signal
generator. During the 4 ms solenoid valve opening, only a small amount
of the mixture (less than 1 % [33]) driven by the pressure difference
flowed into the sampling system, resulting in negligible changes to the
pressure in the combustion chamber. Fig. 2 illustrates the pressure trace
of a typical sampling experiment. To facilitate comparison between
sampling timings across tests with disparate ignition delay times, a
normalized sampling timing, as defined by Eq. (1), was employed. This
normalized timing is the ratio of the solenoid valve trigger timing
τsampling to the mixture ignition delay time τign. As shown in Fig. 2,
τsampling and τign denote the time intervals from the EOC to the timing of
maximum pressure rise rates in the sampling chamber and combustion
chamber, respectively. It is worth noting that τ = 0 is the EOC timing,
and τ = 1 is the ignition timing.
τsampling
τ= (1)
τign
The sampled mixture obtained from each test was then analyzed by
gas chromatography (GC, Agilent 7890B). Ultra-high purity helium
(>99.99 %) was used as the carrier gas for the two detectors. Fig. 3
presents the signal information of the species detected by the two de­
tectors. A flame ionization detector (FID) detector, operating with the
hydrogen/air flame at 250 ◦ C, was used to detect methanol in this study,
while a thermal conductivity detector (TCD), operating at 150 ◦ C, was
employed for the detection of carbon dioxide, nitrous oxide, nitrogen,
carbon monoxide, and ammonia. Detailed description of the sampling
system and gas chromatograph can be found in Ref. [34].
2.3. Test conditions
Four stoichiometric ammonia-methanol/oxygen/argon mixtures
were tested under various thermodynamic conditions in this work,
which were given in Table 1. Based on the relative molar ratio of
ammonia and methanol in the mixture, the four kinds of mixtures were
named by A20 (ammonia 20 %, methanol 80 %), A40 (ammonia 40 %,
methanol 60 %), A80 (ammonia 80 %, methanol 20 %), A95 (ammonia
95 %, methanol 5 %), respectively. Argon was used as the buffer gas with
a dilution ratio of 8 to improve the effective temperature. In the prep­
aration of the mixtures, high purity argon (>99.99 %), oxygen (>99.99
%), methanol (>99 %), and ammonia (>99 %) were filled into a stain­
less tank in accordance with Dalton’s partial pressure law. The mixtures
were left still for more than 2 h to ensure homogeneity [35].
The initial thermodynamic conditions of the experimental mixture
were indicated by the effective pressure (peff) and the effective tem­
perature (Teff), taking into account the heat loss after the end of
Q. Zhang et al. Fuel 368 (2024) 131636

Fig. 1. Schematic of TU-RCM system.

Fig. 2. A typical pressure trace of the RCM sampling experiment.

compression (EOC). The effective pressure (peff) is defined as the average ∫ tmin
1
pressure from the first peak pressure (pmax) to the minimum pressure peff = pdt (2)
(pmin) after the EOC, as shown in Eq. (2). Fig. 2 shows that time 0 is the (tmin − tEOC ) tEOC

time of the EOC, tEOC, and the corresponding pressure is the first peak ∫ Teff ( )
pressure. Teff is defined by Eq. (3) based on isentropic correlation, in­ γ peff
dlnT = ln (3)
corporates the initial temperature (T0), initial pressure (p0), and specific T0 γ− 1 p0
heat ratio (γ).The effective pressures were adjusted to 15, 20 and 25 bar
by changing the initial pressure of the mixture charged into the com­
bustion chamber, and the effective temperatures were varied from 2.4. Simulation method
around 810 K to around 970 K by changing the length of the combustion
chamber. The zero-dimensional homogeneous reactor of CHEMKIN software
was used to calculate the ignition delay times and species information to
verify the mechanisms and do chemical analysis. Two simulation models
were applied: the constant volume (CV) model, which only considers the

3
Q. Zhang et al. Fuel 368 (2024) 131636

Fig. 3. A typical GC chromatogram of the species in the ammonia-methanol compression ignition process.

the experimental results for A80 but considerably different for A95. The
Table 1
calculated results of M4 are also very close to the experimental results
Mixture composition and test conditions.
for A80, but not as good as M3 and M5 in the other three ammonia
nNH3/(nNH3 + peff (bar) Teff (K) Equivalent ratio Dilution ratios. There is no mechanism capable of accurately predicting the
nCH3OH) ratio
ignition delay time of ammonia-methanol blends across different ratios.
φ

20 % (A20) 15/20/ 810–970 1 8 This may stem from a disconnect between applicable conditions of the
40 % (A40) 25 (Pure Ar)
mechanisms and the actual experimental conditions. Under engine-
80 % (A80)
95 % (A95) relevant conditions, the accuracy of the mechanisms in predicting the
ignition delay time of ammonia-methanol fuel in a wide range of pro­
portions needs to be improved. The conclusions drawn from the results
ideal case ignoring the heat loss during combustion, and the volume at peff = 15 bar and 20 bar are the same.
history (VH) model, which takes heat loss into account. The calculation In addition, it is noteworthy that for M3, compared with the calcu­
method for the VH model can be referred to Ref. [31]. Five mechanisms lated results using the CV model, the ignition delay times calculated by
including ammonia and methanol were used for the calculations, as using the VH model are more consistent with the experimental results
shown in Table 2. However, there are currently a limited number of only when the proportion of methanol is lower (A80, A95), while the VH
mechanisms available for ammonia-methanol blends. Among the five results calculated using M5 are consistently more skewed than the re­
mechanisms, only M2 and M3 are dedicatedly developed for ammonia- sults of the CV model. For A95, only M3 successfully calculated the
methanol blends, while the other three mechanisms are not. The ignition delay times using the VH model, while other mechanisms failed
applicability of the five mechanisms to this study will be evaluated in the to yield valid results, because the calculated ignition delay times are
next section. longer than 1 s.

3. Results and discussion 3.1.2. Species sampling results

A80 and A95 were selected for sampling experiments as the
3.1. Experimental results and mechanism validation maximum pressures in the combustion chamber for the other two fuel
blends were much higher than the threshold of the sampling valve. In
3.1.1. Ignition delay time such cases, a too high pressure could make the sampling valve open for
Fig. 4 illustrates the experimental and the calculated results of the too long or directly damage the sampling valve. In a sampling experi­
ignition delay times at peff = 25 bar. The solid lines show the calculated ment, a longer ignition delay time will be affected by heat loss, while a
results using the CV model, while the dashed lines show the results using shorter ignition delay time will lead to increased uncertainty in the
the VH model. It can be observed that for A20 and A40, calculated re­ sampling process [34]. To obtain a suitable ignition delay time, sam­
sults of M5 are most consistent with the experimental results, and the pling experiments for A80 were conducted under the conditions of Teff =
results of M3 are also close to the experimental results. However, for A80 890 K and peff = 25 bar. The average ignition delay time was about 41
and A95, the results obtained from M3 are in better agreement with the ms, and the sampling resolution is 10.25:1 (average ignition delay 41
experimental results. The calculated results using M5 are also close to ms: sampling duration 4 ms). The sampling experiments for A95 were
conducted under the conditions of Teff = 932 K and peff = 25 bar. The
average ignition delay time was about 46 ms, and the sampling resolu­
Table 2 tion was 11.5:1 (average ignition delay 46 ms: sampling duration 4 ms).
Reaction mechanisms for ammonia-methanol oxidation simulation.
It should be noted that the mole fraction calculated from the GC
No. Mechanism Source deviates from the real value of the sampled species due to the existence
M1 Dai et al. Ref. [9] of a dead volume (the volume of the sampling probe) in the sampling
M2 Wang et al. Ref. [25] system. The unreacted gas in the dead volume dilutes the sampled
M3 Li et al. Ref. [29] mixture from the ’adiabatic core region’. A correction coefficient ξ
M4 Li et al. Ref. [36]
defined by Eq. (4) is calculated to compensate for the above-mentioned
M5 Glarborg et al. Ref. [37]

4
Q. Zhang et al.
Fig. 4. Comparison of experimental and calculated results of ignition delay time at peff = 25 bar.
dilution effect, where pdead, Tdead and Vdead represent the pressure,
temperature and volume of the dead volume, respectively. psampling,
Tsampling and Vsampling represent the pressure, temperature and volume of
the sampling chamber, respectively. The detailed calculation procedure
of ξ and its uncertainty can be found in Ref. [33,38] and the results are
shown in Fig. 5 and Fig. 6.
The real value of species concentration in ’adiabatic core region’, χ i,
core, was calibrated by Eq. (5) using the original value χ i,samping (calcu­
lated by GC signal). For all species except the initial reactants ammonia
and methanol involved in this work, χ i,dead is 0, and the χ i,dead of
ammonia and methanol is the same as the concentration in the initial
mixture.
( )− 1
pdead ⋅Vdead psampling ⋅Vsampling
ξ= ⋅ (4)
Tdead Tsampling
χ i,core *(1 − ξ) + χ i,dead *ξ = χ i,sampling
The sampling results were averaged since the sampling valve opened
for 4 ms. And the initial temperature fluctuation and partial pre-reaction
in the compression process will affect the measurement results of the
ignition delay time. Therefore, it is necessary to consider the uncertainty
of the sampling time. This can be determined using the method
described in Ref. [39], as shown in Eq. (6). In this equation, δτsampling,
τign, τ, and δτign represents half of the sampling valve opening duration,
the overall ignition delay time, the normalized sampling timing, and the
Fuel 368 (2024) 131636
uncertainty of the measurement of the ignition delay time, respectively.
The detailed calculation method for δτign can be found in Ref. [39,40].
The obtained uncertainties of sampling times are shown in Fig. 5 and
Fig. 6.
δτsampling τ
δτ = − ⋅δτ (6)
τign τign ign
Based on the calculated results of the ignition delay time, mecha­
nisms M3 (Li et al.) and M5 (Glarborg et al.) were selected to numeri­
cally calculate the evolution of intermediate species concentration. The
results, as shown in Fig. 5 and Fig. 6, indicate that both the two mech­
anisms can approximately predict the trend of intermediate species
concentration, and M3 has better performance. However, both the two
mechanisms exhibit noticeable deviations in predicting the final con­
sumption of CO and the final production of CO2, which may be attrib­
uted to the incomplete consumption path of CO in the two mechanisms.
(5)
These discrepancies do not have an impact on the analysis of the con­
sumption of fuels and their interactive reactions during the ignition
process, which are the focus of this study. Therefore, subsequent nu­
merical calculations are based on M3 due to its accuracy in predicting
both the ignition delay time and intermediate species.
5
Q. Zhang et al.
Fig. 5. Sampling results and simulation results of the intermediate species of A80.
3.2. Ignition-enhancing effect of methanol on ammonia
3.2.1. Reduction of ignition delay time
The ignition delay times of ammonia-methanol blended fuel under
four ratios are shown in Fig. 7. It is evident that with an increase in the
proportion of methanol, the ignition delay time is significantly reduced,
suggesting that the addition of methanol improves the reactivity of the
fuel. However, when the proportion of methanol surpassed 20 %, there
is little variation in the ignition delay times, consistent with the results
reported by Li et al. [29].
It is worth noting that pure ammonia did not ignite in the tempera­
ture range of 810 K-970 K and the lowest ignition temperature of pure
ammonia was about 1050 K. This indicates that adding methanol is
efficient in lowering the minimum ignition temperature of ammonia.
3.2.2. ROP and sensitivity of OH radical
Given the importance of the OH radical accumulation in te ignition
process and its significant contribution to the consumption of methanol
and ammonia [29], the rate of production (ROP) of OH radical was
calculated using M3, as shown in Fig. 8. The calculation conditions for
the four blended fuels were Teff = 890 K and peff = 25 bar. It can be
observed that an increase in methanol proportion results in an increase
in the peak value of both the OH fraction and its ROP, demonstrating
enhanced reactivity of the mixture during the ignition process.
The sensitivity of OH radical at the ignition timing were calculated to
further analyze the leading reactions controlling its generation. The top
five reactions most sensitive to the generation of OH radical are selected
to be shown in Fig. 9. The sensitivity results indicate the significant role
of methanol reactions in OH radical generation. When the proportion of
methanol is 20 % or more (A80, A40, A20), R123 is always the most
6
Fuel 368 (2024) 131636
sensitive reaction for OH radical generation, except for R21 of H2O2
decomposition to OH. Even for A95, which has the smallest proportion
of methanol, R119 and R123 remain among the top five reactions with
relatively large sensitivity coefficients. As the proportion of ammonia
decreases, the influence of ammonia-related reactions on OH radical
generation gradually decreases. In the case of A40, only one of the first
five reactions (R1015) is related to ammonia, with a very small sensi­
tivity coefficient. For A20, there are no reactions directly related to
ammonia among the first five reactions. This means that methanol
significantly enhances the production of OH radical, thereby boosting
the overall reactivity of the mixture.
3.3. Fuel consumption patterns
Different fuel consumption patterns of A80 and A95 were observed
from the sampling results. As shown in Fig. 5, for A80, in the early stage
of the ignition process (normalized timing < 0.8), methanol consumes
slowly while ammonia shows almost no consumption. When the
normalized timing is close to 1, most of both ammonia and methanol
were rapidly consumed. The intermediate species CO and N2O begin to
accumulate slowly at the normalized time of around 0.6, with peak
concentrations appearing just before the ignition timing (normalized
timing of around 0.9), and then are rapidly consumed. The majority of
final products CO2 and N2 are generated at the moment of ignition, with
very little production in the early stage of the ignition process. For A95,
as shown in Fig. 6, methanol begins to be consumed at a certain rate
from the EOC to the ignition timing, without any obvious instantaneous
consumption process. This may be attributed to the reduction of the
initial concentration of methanol. However, ammonia experiences slow
consumption in the early stage of the ignition process and then is rapidly
Q. Zhang et al. Fuel 368 (2024) 131636

Fig. 6. Sampling results and simulation results of the intermediate species of A95.

Fig. 7. Experimental results of ignition delay time.

consumed when close to the ignition timing. Different from A80, the
intermediate species CO and N2O of A95 are slowly generated from the
EOC, then the generation rate increases slightly after the normalized
time of around 0.6. Finally, CO and N2O are consumed rapidly at the
moment of ignition. The generation mode of final products CO2 and N2
are similar to that of A80.
M3 was used to calculate the ROP of NH3, CH3OH and their inter­
mediate species to further analyze the reasons for the different fuel
consumption rates of A80 and A95. Li et al. pointed out that the inter­
action between NH2 and CH2O has a significant inhibitory effect on the
consumption of NH3 [29]. Hence, the ROP of CH3OH, CH2O, NH3 and
NH2 were examined, as illustrated in Fig. 10 and Fig. 11. The five

7
Q. Zhang et al. Fuel 368 (2024) 131636

Fig. 8. Molar fraction and ROP of OH radical.

Fig. 9. Sensitivity to OH radical formation.

reactions listed in the figures are the ones with the highest ROP from the
EOC to the ignition timing. Dash lines in the figures indicate reactions
involving both carbon and nitrogen species, while solid lines represent
reactions involving only carbon or nitrogen species.
The ROP of key reactions in Fig. 10 indicates that NH2 can generate
from NH3 by R1015, but because of the presence of CH3OH, the inter­
mediate species CH2O continuously reduces NH2 to NH3 by R1537,
which significantly inhibits the consumption of NH3. That is why NH3
does not consume in the early stage for A80 as mentioned above. R1017
also inhibits NH3 consumption, but this reaction is independent of
carbon-containing species and the reaction rate is much less than that of
R1537. Meanwhile, no reaction inhibits the consumption of CH3OH,
which mainly converts to CH2OH via R119, and further generates CH2O
via R130. The most important consumption reaction of CH2O is R1357,
in which CH2O is further dehydrogenated to HCO, reducing NH2 to NH3,
which indicates that NH2 promotes the consumption of CH3OH. That is
why CH3OH begin to be consumed from the early stage of the ignition
process for A80.
For A95, the ROP of key reactions in Fig. 11 indicates that most of
NH3 converts to NH2 through R1015. Although there are still reactions
(R1017 et al.) inhibiting NH3 consumption, these reactions are inde­
pendent of carbon-containing species, and their rates are very low. The
major consumption reactions (R1023, etc.) of NH2 are also independent
of carbon-containing species. For CH3OH, no reactions impede its con­
sumption, similar to that for A80. The main consumption reactions are
R119, R1793 and R1794. R1793 and R1794 are interactive reactions

8
Q. Zhang et al. Fuel 368 (2024) 131636

Fig. 10. ROP of key reactions of some species for A80.

Fig. 11. ROP of key reactions of some species for A95.

between CH3OH and NH2, where CH3OH dehydrogenates, and NH2 is inhibits the consumption of NH3. However, the lower reaction rates of
reduced to NH3. Therefore, in the case of A95, NH2 still promotes the R1793 and R1794 compared to other reactions of NH3 limit their
consumption of CH3OH while the presence of CH3OH, in turn, still inhibitory effect on NH3 consumption. As for the consumption reactions

9
Q. Zhang et al.
of CH2O, R1357 exhibits the highest reaction rate, which involves NH2.
CH2O dehydrogenates and converts to HCO while NH2 is reduced to
NH3, further supporting the conclusion that NH2 promotes the con­
sumption of CH3OH. However, R1357 is not dominant for NH2 and NH3,
as illustrated in Fig. 11. The inhibitory effect of CH3OH on NH3 con­
sumption is not apparent. That is why both NH3 and CH3OH are slowly
consumed from the early stage of the ignition process for A95 as
mentioned above.
In summary, the consumption of ammonia was significantly inhibi­
ted by methanol and its intermediate species CH2O at a methanol pro­
portion of 20 % (A80). Conversely, the consumption of methanol was
promoted by ammonia and its intermediate species NH2. At a lower
methanol ratio (A95), ammonia still promoted the consumption of
methanol. However, although methanol and CH2O still inhibited the
consumption of ammonia, this inhibitory effect was not evident due to
the low concentration of methanol.
3.4. Interactive reaction paths between ammonia and methanol
Analyses of reaction flux were conducted for the four ammonia-
methanol blends based on the ROP calculated using M3. This aimed to
further compare the reaction paths of ammonia, methanol, and their
intermediate species. For consistency with experimental conditions, the
calculation conditions for A95 were Teff = 932 K and peff = 25 bar while
the conditions of the other three kinds of blends were Teff = 890 K and
peff = 25 bar. It was found that there was minimal impact on the reaction
flux when the temperature changed from 890 K to 932 K for A95 fuel.
The timing of 50 % methanol consumption and ignition timing were
selected to represent the early and late stage of the ignition process,
Fig. 12. Integrated reaction flux at the timing of 50% methanol consumption.
10
Fuel 368 (2024) 131636
respectively. The corresponding reaction fluxes are presented in Fig. 12
and Fig. 13, with colored reaction paths for clear distinction. Carbon-
only reaction paths were depicted by brown arrows, nitrogen-only re­
action paths by blue arrows, and carbon–nitrogen interaction paths by
orange arrows. The species annotated alongside the arrows are the re­
actants of the species at the start of the arrows. The contribution of each
species is indicated by the percentage number, with different colors
representing different proportions of fuel. The dashed arrows indicate
that the species at the start is insignificant (the reaction flux of upstream
species is less than 5 %) at low methanol proportions but becomes sig­
nificant at high methanol proportions. It is worth noting that the reac­
tion paths of nitrogen-containing species that does not participate in the
interaction are not included in Fig. 12 and Fig. 13 since this study fo­
cuses on the consumption of fuel and the interaction between carbon-
containing and nitrogen-containing species.
Consistent with the conclusion in Section 3.3, Fig. 12 reveals that in
the early stage of the reaction (when methanol consumption is 50 %),
the consumption of ammonia is inhibited. This inhibition is manifested
by methanol and its intermediate species CH2O reducing NH2 to
ammonia. With the increase of methanol ratio, the reduction path of
NH2 to NH3 by CH2O is gradually enhanced. With an increase in the
proportion of ammonia, NH2 will promote the consumption of meth­
anol, and the reactions of methanol and CH2O with NH2 gradually
dominate. The contribution of the reaction of methanol with NH2 in­
creases from < 5 % to 41.3 % and the reaction of CH2O with NH2 in­
creases from 14.5 % to 99.1 %. Conversely, the reaction between NH2
and methanol weakens as the proportion of ammonia decreases, but
methanol can still be consumed by the reaction with OH radical. Addi­
tionally, an interaction is observed between CO and N2O with both
Q. Zhang et al.
Fig. 13. Integrated reaction flux at the ignition timing.
species contributing to each other’s consumption. This interaction is
enhanced with the increase of the proportion of ammonia.
The interaction between ammonia and methanol described previ­
ously persists until the ignition timing, as depicted in Fig. 13. The dif­
ference is that, at the ignition timing, the significance of CH2O-related
reactions decreases (<5%) for NH2 when the proportion of methanol is
low (A95). In contrast, the reaction between NH2 and HO2 intensifies,
which also inhibits the consumption of ammonia. For A80 and A95,
HNCO and NCO are generated. The generation of HNCO is a result of the
reaction between CO and NH2. The subsequent evolution path of HNCO
and NCO leads to the final production of CO2 and N2. Therefore, the
interaction between CO and NH2 promoted fuel consumption, and this
interaction was enhanced with the increase of ammonia proportion.
However, it is crucial to note the toxicity of HNCO and NCO. If the re­
actions are incomplete, they may cause more severe emission problems.
4. Conclusions
This study examined the ignition characteristics of ammonia-
methanol blended fuels with four mixing ratios under stoichiometric
conditions at peff = 15/20/25 bar and TEOC = 810–970 K. The key
findings from experiments and simulations can be summarized as
follows:
(1) The addition of methanol lowered the ignition temperature and
shortened the ignition delay time of ammonia. However, there
11
Fuel 368 (2024) 131636
was little difference in ignition delay times when the proportion
of methanol exceeded 20 %. The peak value of OH radical
increased with methanol proportion, indicating the significant
effect of methanol on the overall reactivity of the mixture.
(2) Methanol and ammonia showed different consumption patterns
at different mixing ratios. For A80, methanol started to consume
slowly at the early stage of the ignition process, while ammonia
showed no consumption. This suggests significant inhibition of
ammonia by methanol and its intermediate species CH2O, as
evidenced by the ROP analysis. As the ignition timing
approached, both methanol and ammonia were consumed
rapidly. However, for A95, methanol consumed at a relatively
steady rate from the EOC all the way to the ignition timing,
without any obvious instantaneous consumption process. In
contrast, ammonia experienced slow consumption during the
early stage of the ignition process, which is due to the weakened
inhibition effect of methanol and CH2O.
(3) The consumption of ammonia in both early and late stages of the
ignition process was inhibited by methanol and its intermediate
species CH2O, and the reduction path of NH2 to NH3 by CH2O was
gradually enhanced with increasing methanol proportion. As the
proportion of ammonia increased, NH2 would promote the con­
sumption of methanol. Additionally, it was observed that CO
interacted with NH2 and N2O, which promoted the consumption
of each other. This interaction was enhanced with increasing
ammonia proportion.
Q. Zhang et al.
CRediT authorship contribution statement
Qihang Zhang: Writing – original draft, Software, Methodology,
Investigation, Formal analysis, Data curation. Ridong Zhang: Writing –
review & editing, Investigation. Yunliang Qi: Writing – review &
editing, Validation, Software, Methodology, Formal analysis. Zhi Wang:
Conceptualization, Project administration, Supervision.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Data availability
Data will be made available on request.
Acknowledgment
This study was supported by the National Natural Science Founda­
tion of China (Grant Nos.: T2341002, T2241003, and 52076118) and
Tsinghua-Toyota Joint Research Fund (Grant No.: 20213930001).
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